CN116657162B - Preparation method of high-purity ammonium persulfate - Google Patents
Preparation method of high-purity ammonium persulfate Download PDFInfo
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- CN116657162B CN116657162B CN202310546852.XA CN202310546852A CN116657162B CN 116657162 B CN116657162 B CN 116657162B CN 202310546852 A CN202310546852 A CN 202310546852A CN 116657162 B CN116657162 B CN 116657162B
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- ammonium persulfate
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- ammonium polyphosphate
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910001870 ammonium persulfate Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 47
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 39
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 39
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 37
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 37
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 37
- 238000007747 plating Methods 0.000 claims abstract description 35
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 11
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000007086 side reaction Methods 0.000 claims abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 27
- 238000005868 electrolysis reaction Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 229920000137 polyphosphoric acid Polymers 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 5
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- FKNWMNQVNAGIDF-UHFFFAOYSA-N copper platinum titanium Chemical compound [Ti][Cu][Pt] FKNWMNQVNAGIDF-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003051 hair bleaching agent Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/29—Persulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method of high-purity ammonium persulfate, which comprises the steps of firstly electrolyzing ammonium sulfate by an electrolytic method to prepare ammonium persulfate, modifying an anode additive ammonium polyphosphate by using N-methylethanolamine and gamma-propyl trimethyl siloxane, and preparing the ammonium persulfate with purer concentration by using refined titanium plating copper plating platinum as an anode and graphite as a cathode. The modified ammonium polyphosphate has a better function of inhibiting hydrogen evolution side reaction, and can also carry out complex reaction with heavy metal ions in electrolyte, so that ammonium persulfate is not easy to decompose. Meanwhile, the modified ammonium polyphosphate of the polyphosphoric acid is used as an anode additive, so that the modified ammonium polyphosphate is more environment-friendly, and waste gas and waste liquid polluting the environment are not generated. The refined titanium plating copper plating platinum is used as an anode of the electrolytic cell, has higher corrosion resistance and oxidation resistance, higher oxygen evolution overpotential and better electrocatalytic activity, and also ensures that the current efficiency is more excellent.
Description
Technical Field
The invention relates to the field of preparation of ammonium persulfate, in particular to preparation of ammonium persulfate by an electrolytic method, and particularly relates to preparation of high-purity ammonium persulfate.
Background
Ammonium persulfate is colorless monoclinic crystal or white powdery crystal, is easy to dissolve in water, and is acidic in aqueous solution. Ammonium persulfate is a dangerous article, and when ammonium persulfate is mixed with certain organic matters with strong reducibility, fire or explosion can be initiated. Industrial ammonium persulfate has wide application in the fields of chemical industry, light industry, electronics, petroleum and food industry and the like, and is mainly used as an oxidant, a polymerization promoter for high-molecular polymerization, a polymerization agent for vinyl chloride compounds, an initiator for organic synthesis, an etchant for the electronics industry, a desizing agent for the textile industry, an additive for petroleum fracturing agents, an oxidant for aniline dyes, a vulcanizing agent for rubber, a swimming pool disinfectant, wastewater treatment, a dry bleaching agent for a washing and dyeing shop, a hair bleaching agent and the like.
At present, the anthraquinone method for preparing ammonium persulfate still exists in the industry, but the purity of ammonium persulfate produced by the anthraquinone method is relatively low and the cost is relatively high. In addition, the method has great environmental pollution in the production process and does not have market competitiveness. Therefore, the preparation method of ammonium persulfate mainly takes an electrolytic method, namely the electrolytic method is to electrolyze an ammonium sulfate aqueous solution to generate ammonium persulfate, and the ammonium persulfate crystal is separated out through freezing the solution.
Disclosure of Invention
Aiming at the problems, the modified ammonium polyphosphate is used as a novel anode additive, so that the side reaction of hydrogen evolution of the anode is reduced, and the current efficiency is improved; and the refined titanium copper plating platinum is used as the anode of the electrolytic cell, so that the electrolytic cell has higher corrosion resistance, oxidation resistance, oxygen evolution overpotential and electrocatalytic activity, reduces the consumption of noble metals and ensures that the current efficiency is more excellent. The preparation process is simple and convenient to operate, and the yield and purity of ammonium persulfate are further improved by using the modified ammonium polyphosphate prepared by the method and the refined titanium copper plating platinum as the anode of the electrolytic cell. The preparation method comprises the following specific steps:
s1, adding 25% sulfuric acid into a reaction container, stirring while adding ammonia water until the pH value of the solution is 5-6, stopping dropwise adding ammonia water, continuing stirring and reacting for a period of time, and repeatedly filtering and crystallizing to prepare an ammonium sulfate product;
s2, dissolving the product in deionized water to prepare an ammonium sulfate solution with the mass concentration of 10%, placing the solution in a constant-temperature water bath at 60 ℃ for recrystallization, and placing the solution in a Buchner funnel for suction filtration. Drying for 24 hours in a vacuum drying oven at 50-70 ℃ to obtain a final ammonium sulfate product;
s3, preparing electrolyte: adding an ammonium sulfate solution with the concentration of 0.50g/ml and a sulfuric acid with the concentration of 25% in a volume ratio of 1:1, placing in a beaker, and uniformly mixing to prepare an electrolyte;
s4, placing ammonium polyphosphate with the mass concentration of 30% into a beaker, adding a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 8:2, adding N-methylethanolamine with the mass concentration of 1%, and stirring for reacting for 0.5-1 h to obtain ammonium polyphosphate-N-methylethanolamine salt;
s5, dispersing 6% of gamma-propyl trimethyl siloxane in a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 9:1, stirring for 8min at 30 ℃, adding ammonium polyphosphate-N-methyl ethanolamine salt in the steps, stirring and dispersing, carrying out suction filtration after 1h, and drying the obtained solid in a drying box at 105 ℃ to obtain white powdery modified ammonium polyphosphate; the modified ammonium polyphosphate can better inhibit hydrogen evolution side reaction, and can also carry out complex reaction with heavy metal ions in electrolyte, so that ammonium persulfate is not easy to decompose, and the ammonium persulfate has a certain effect on stabilizing the ammonium persulfate.
S6, carrying out electrolysis in a platy diaphragm electrolytic tank, wherein refined titanium plating copper plating platinum is used as an anode, and a mixed solution of ammonium sulfate and sulfuric acid is used as an anolyte; graphite is used as a cathode, and sulfuric acid with the concentration of 25% is used as catholyte; the anode additive was modified ammonium polyphosphate with a mass of 0.03 g. And (3) carrying out constant current electrolysis experiments at the electrolysis temperature of 35 ℃ for 4 hours to prepare ammonium persulfate.
Preferably: in the step S1, ammonia water is added while stirring until the pH value of the solution is 5.
Preferably: the temperature in the vacuum drying oven in the step S2 is 70 ℃.
Preferably: the concentration of ammonium sulfate in the step S3 is 0.50g/ml.
Preferably: in the step S4, ammonium polyphosphate is purchased from Changfeng chemical industry, and N-methylethanolamine is purchased from Chemicals.
Preferably: the gamma-propyl trimethyl siloxane in the step S5 is purchased from Jian Shuangjia chemical industry.
Preferably: in the step S6, refined titanium copper plating and platinizing are used as anodes, and the ratio of titanium, copper and platinum alloy is 5:2:3, 0.03g of modified ammonium polyphosphate is added, the electrolysis time is 4 hours, and the electrolysis voltage is 5.5V.
Preferably: the diaphragm of the plate diaphragm electrolytic cell in the step S6 is prepared by taking a film of a binary copolymer of polyethylene and ethylene-octene copolymer as a base film, divinylbenzene as a cross-linking agent and benzoyl peroxide as an initiator, and is purchased from Yu Aiyu Qi film technology Co.
The invention has the beneficial effects that:
1. the invention prepares high-purity ammonium persulfate, when the electrolytic method is used for preparing ammonium persulfate, refined titanium plating copper plating platinum is used as an anode, and graphite is used as a cathode. The refined titanium plating copper plating platinum serving as an anode has higher corrosion resistance and oxidation resistance, higher oxygen evolution overpotential and better electrocatalytic activity. This is because there is a synergistic effect between titanium, copper and platinum, making the fine titanium plated copper plated platinum electrode more excellent in electrochemical performance.
2. The ammonium persulfate with higher purity is prepared by using the modified ammonium polyphosphate as an anode additive. The modified ammonium polyphosphate has certain complexing capacity besides inhibiting oxygen precipitation, and can complex heavy metal ions in electrolyte, so that ammonium persulfate is stabilized, is not easy to decompose, and does not generate gas and waste liquid polluting the environment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a SEM image at 30 μm magnification of a brush-plated titanium platinum electrode of the invention.
FIG. 2 is a SEM image at 30 μm magnification of a fine titanium plated copper plated platinum electrode of the present invention.
FIG. 3 is the effect of the different electrodes of the present invention on the purity of ammonium persulfate in example 2 and comparative examples 5 and 6.
FIG. 4 shows the effect of the different conditions of examples 2, 3 and comparative examples 7 to 10 of the present invention on the purity of ammonium persulfate.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the present patent.
Example 1
S1, adding 25% sulfuric acid into a reaction container, stirring while adding ammonia water until the pH value of the solution is 5, stopping dropwise adding ammonia water, continuing stirring and reacting for a period of time, repeatedly filtering, and crystallizing to prepare an ammonium sulfate product;
s2, dissolving the product in deionized water to prepare an ammonium sulfate solution with the mass concentration of 10%, placing the solution in a constant-temperature water bath at 60 ℃ for recrystallization, and placing the solution in a Buchner funnel for suction filtration. Drying in a vacuum drying oven at 70 ℃ for 24 hours to obtain a final ammonium sulfate product;
s3, preparing electrolyte: adding an ammonium sulfate solution with the concentration of 0.50g/ml and a sulfuric acid with the concentration of 25% in a volume ratio of 1:1, placing in a beaker, and uniformly mixing to prepare an electrolyte;
s4, placing ammonium polyphosphate (Changfeng chemical industry) with the mass concentration of 30% into a beaker, adding a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 8:2, adding N-methylethanolamine (cover chemical industry) with the mass concentration of 1%, and stirring for reacting for 1h to obtain ammonium polyphosphate-N-methylethanolamine salt;
s5, dispersing 6% of gamma-propyl trimethyl siloxane (Jian Shuangchemical) in a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 9:1, stirring for 5min at 30 ℃, adding ammonium polyphosphate-N-methyl ethanolamine salt in the steps, stirring and dispersing, carrying out suction filtration after 1h, and drying the obtained solid in a drying box at 90 ℃ to obtain white powdery modified ammonium polyphosphate;
s6, carrying out electrolysis in a platy diaphragm electrolytic tank, wherein refined titanium plating copper plating platinum is used as an anode, and a mixed solution of ammonium sulfate and sulfuric acid is used as an anolyte; graphite is used as a cathode, and sulfuric acid with the concentration of 25% is used as catholyte; the anode additive was modified ammonium polyphosphate with a mass of 0.03 g. And (3) carrying out constant current electrolysis experiments at the electrolysis temperature of 35 ℃ for 4 hours to prepare ammonium persulfate.
Comparative example 1 an ammonium sulfate solution having a concentration of 0.40g/ml was added in step S3, and the rest was the same as in example 1.
Comparative example 2 an ammonium sulfate solution having a concentration of 0.45g/ml was added in step S3, and the rest was the same as in example 1.
Comparative example 3 an ammonium sulfate solution having a concentration of 0.55g/ml was added in the step S3, and the rest was the same as in example 1.
Comparative example 4 an ammonium sulfate solution having a concentration of 0.60g/ml was added in step S3, and the rest was the same as in example 1.
TABLE 1
Table 1 is a data table of the effect of adding ammonium sulfate solutions of different concentrations on the purity of the prepared ammonium persulfate. After the electrolysis is finished, taking an anode solution, taking an excessive KI and starch saturated solution as indicators, taking a sodium sulfate solution as a titration agent, and measuring the purity of ammonium persulfate by a quantitative analysis method. As can be seen from the table, as the concentration of the ammonium sulfate solution increases, the purity of ammonium persulfate increases. However, when an ammonium sulfate solution having a concentration of 0.50g/ml is added, the increase in the purity of ammonium persulfate is greatest, and then an ammonium sulfate solution having a concentration of 0.55g/ml or a ammonium sulfate solution having a concentration of 0.60g/ml is added, the increase in the purity of ammonium persulfate is slow. This is because, although the concentration of ammonium sulfate is increasing, the amount of sulfuric acid in which the catholyte is 25% in concentration is fixed in the fine titanium copper plating platinized anode, so that the increase is slow. As a result, ammonium sulfate solution having a concentration of 0.50g/ml was added to obtain ammonium persulfate having the best purity.
Example 2
S1, adding 25% sulfuric acid into a reaction container, stirring while adding ammonia water until the pH value of the solution is 5, stopping dropwise adding ammonia water, continuing stirring and reacting for a period of time, repeatedly filtering, and crystallizing to prepare an ammonium sulfate product;
s2, dissolving the product in deionized water to prepare an ammonium sulfate solution with the mass concentration of 10%, placing the solution in a constant-temperature water bath at 60 ℃ for recrystallization, and placing the solution in a Buchner funnel for suction filtration. Drying in a vacuum drying oven at 70 ℃ for 24 hours to obtain a final ammonium sulfate product;
s3, preparing electrolyte: adding an ammonium sulfate solution with the concentration of 0.50g/ml and a sulfuric acid with the concentration of 25% in a volume ratio of 1:1, placing in a beaker, and uniformly mixing to prepare an electrolyte;
s4, placing ammonium polyphosphate (Changfeng chemical industry) with the mass concentration of 30% into a beaker, adding a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 8:2, adding N-methylethanolamine (cover chemical industry) with the mass concentration of 1%, and stirring for reacting for 1h to obtain ammonium polyphosphate-N-methylethanolamine salt;
s5, dispersing 6% of gamma-propyl trimethyl siloxane (Jian Shuangchemical) in a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 9:1, stirring for 5min at 30 ℃, adding ammonium polyphosphate-N-methyl ethanolamine salt in the steps, stirring and dispersing, carrying out suction filtration after 1h, and drying the obtained solid in a drying box at 90 ℃ to obtain white powdery modified ammonium polyphosphate;
s6, carrying out electrolysis in a platy diaphragm electrolytic tank, wherein refined titanium plating copper plating platinum is used as an anode, and a mixed solution of ammonium sulfate and sulfuric acid is used as an anolyte; graphite is used as a cathode, and sulfuric acid with the concentration of 25% is used as catholyte; the anode additive was modified ammonium polyphosphate with a mass of 0.03 g. And (3) carrying out constant current electrolysis experiments at the electrolysis temperature of 35 ℃ for 4 hours to prepare ammonium persulfate.
Comparative example 5 the titanium-platinum-plated anode was brushed in step S4, and the rest was the same as in example 2.
Comparative example 6 platinum metal was used as the anode in step S4, and the rest was the same as in example 2.
FIG. 3 is a bar graph of the different purities of ammonium persulfate produced at different electrodes. After the electrolysis was completed, the purity of ammonium persulfate was measured by a quantitative analysis method. The graph shows that the current efficiency is that the brush plating titanium platinum is less than the platinum and less than the fine plating titanium copper platinum. FIG. 1 is a SEM image at 30 μm magnification of a brush-plated titanium platinum electrode of the invention. FIG. 2 is a SEM image at 30 μm magnification of a fine titanium plated copper plated platinum electrode of the present invention. From the figure, it can be seen that the enlarged SEM of the brush-plated titanium-plated platinum electrode has obvious cracks, while the enlarged SEM of the finish-plated titanium-plated copper-plated platinum electrode is regularly and densely arranged. The refined titanium plating copper plating platinum electrode has higher oxygen evolution overpotential and better electrocatalytic activity, and is an ideal anode in the reaction process of electrosynthesis of ammonium persulfate. Therefore, the titanium, copper and platinum have a synergistic effect, so that the fine titanium plating copper plating platinum plating electrode has more excellent electrochemical performance, and the fine titanium plating copper plating platinum plating electrode is selected to be used as an anode material for synthesizing ammonium persulfate by an electrolytic method.
Example 3
S1, adding 25% sulfuric acid into a reaction container, stirring while adding ammonia water until the pH value of the solution is 5, stopping dropwise adding ammonia water, continuing stirring and reacting for a period of time, repeatedly filtering, and crystallizing to prepare an ammonium sulfate product;
s2, dissolving the product in deionized water to prepare an ammonium sulfate solution with the mass concentration of 10%, placing the solution in a constant-temperature water bath at 60 ℃ for recrystallization, and placing the solution in a Buchner funnel for suction filtration. Drying in a vacuum drying oven at 70 ℃ for 24 hours to obtain a final ammonium sulfate product;
s3, preparing electrolyte: adding an ammonium sulfate solution with the concentration of 0.50g/ml and a sulfuric acid with the concentration of 25% in a volume ratio of 1:1, placing in a beaker, and uniformly mixing to prepare an electrolyte;
s4, placing ammonium polyphosphate (Changfeng chemical industry) with the mass concentration of 30% into a beaker, adding a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 8:2, adding N-methylethanolamine (cover chemical industry) with the mass concentration of 1%, and stirring for reacting for 1h to obtain ammonium polyphosphate-N-methylethanolamine salt;
s5, dispersing 6% of gamma-propyl trimethyl siloxane (Jian Shuangchemical) in a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 9:1, stirring for 5min at 30 ℃, adding ammonium polyphosphate-N-methyl ethanolamine salt in the steps, stirring and dispersing, carrying out suction filtration after 1h, and drying the obtained solid in a drying box at 90 ℃ to obtain white powdery modified ammonium polyphosphate;
s6, carrying out electrolysis in a platy diaphragm electrolytic tank, wherein refined titanium plating copper plating platinum is used as an anode, and a mixed solution of ammonium sulfate and sulfuric acid is used as an anolyte; graphite is used as a cathode, and sulfuric acid with the concentration of 25% is used as catholyte; the anode additive was modified ammonium polyphosphate with a mass of 0.03 g. And (3) carrying out constant current electrolysis experiments at the electrolysis temperature of 35 ℃ for 4 hours to prepare ammonium persulfate.
Comparative example 7 in step S6, 0.01g of modified ammonium polyphosphate was added, respectively, and the rest was the same as in example 3.
Comparative example 8 0.02g of modified ammonium polyphosphate was added in the step S6, respectively, and the rest was the same as in example 3.
Comparative example 9 in step S6, 0.04g of modified ammonium polyphosphate was added, respectively, and the rest was the same as in example 3.
Comparative example 10 in step S6, 0.05g of modified ammonium polyphosphate was added, respectively, and the rest was the same as in example 3.
TABLE 2
Table 2 is a data table of the effect of adding different mass modified ammonium polyphosphate on ammonium persulfate purity. After the electrolysis is finished, taking an anode solution, taking an excessive KI and starch saturated solution as indicators, taking a sodium sulfate solution as a titration agent, and measuring the purity of ammonium persulfate by a quantitative analysis method. In the reaction for preparing ammonium persulfate through electrolysis, hydrogen evolution side reaction is an important reason for reducing the current efficiency of generating ammonium persulfate by an anode. The modified ammonium polyphosphate can better inhibit hydrogen evolution side reaction, and can also carry out complex reaction with heavy metal ions in electrolyte, so that ammonium persulfate is not easy to decompose, and the ammonium persulfate has a certain effect on stabilizing the ammonium persulfate. Meanwhile, the modified ammonium polyphosphate of the polyphosphoric acid is used as an anode additive, so that the modified ammonium polyphosphate is more environment-friendly, and waste gas and waste liquid polluting the environment are not generated. As can be seen from the table, the addition of modified ammonium polyphosphate having a mass of 0.03g produced ammonium superphosphate having the highest purity, either too high or too low, was not effective in preventing the formation of oxygen.
Claims (6)
1. A preparation method of high-purity ammonium persulfate is characterized by comprising the following steps of: the specific steps are as follows:
s1, adding 25% sulfuric acid by mass into a reaction container, adding ammonia water while stirring until the pH value of the solution is 5-6, stopping dropwise adding the ammonia water, continuing stirring for reacting for a period of time, and repeatedly filtering and crystallizing to prepare an ammonium sulfate product;
s2, dissolving the product in deionized water to prepare an ammonium sulfate solution with the mass concentration of 10%, placing the solution in a constant-temperature water bath at 60 ℃ for recrystallization, placing the solution in a Buchner funnel for suction filtration, and then drying 24h in a vacuum drying oven at 50-70 ℃ to obtain a final ammonium sulfate product;
s3, preparing electrolyte: adding an ammonium sulfate solution with the concentration of 0.50g/ml and a sulfuric acid with the concentration of 25% in a volume ratio of 1:1, placing in a beaker, and uniformly mixing to prepare an electrolyte;
s4, placing ammonium polyphosphate with the mass concentration of 30% in a beaker, adding a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 8:2, adding N-methylethanolamine with the mass concentration of 1%, and stirring for reacting for 0.5-1 h to obtain ammonium polyphosphate-N-methylethanolamine salt;
s5, dispersing 6% of gamma-propyl trimethyl siloxane in a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 9:1, stirring for 5-8 min at 30 ℃, adding ammonium polyphosphate-N-methyl ethanolamine salt in the steps, stirring and dispersing, carrying out suction filtration after 1h, and drying the obtained solid in a drying box at 90-110 ℃ to obtain white powdery modified ammonium polyphosphate; the modified ammonium polyphosphate can better inhibit hydrogen evolution side reaction, and can also carry out complex reaction with heavy metal ions in electrolyte, so that ammonium persulfate is not easy to decompose, and the ammonium persulfate has a certain effect on stabilizing the ammonium persulfate;
s6, carrying out electrolysis in a platy diaphragm electrolytic tank, wherein refined titanium plating copper plating platinum is used as an anode, and a mixed solution of ammonium sulfate and sulfuric acid is used as an anolyte; graphite is used as a cathode, and sulfuric acid with the concentration of 25% is used as catholyte; and the anode additive is modified ammonium polyphosphate with the mass of 0.01 g-0.05 g, the electrolysis temperature is 35 ℃, the electrolysis time is 2-5 h, and constant current electrolysis experiments are carried out to prepare ammonium persulfate.
2. The method for producing high-purity ammonium persulfate according to claim 1, wherein: in the step S1, ammonia water is added while stirring until the pH value of the solution is 5.
3. The method for producing high-purity ammonium persulfate according to claim 1 or 2, wherein: the temperature in the vacuum drying oven in the step S2 is 70 ℃.
4. The method for producing high-purity ammonium persulfate according to claim 3, wherein: in the step S4, 2g N-methylethanolamine is added and stirred for reaction for 1h.
5. The method for producing high-purity ammonium persulfate according to claim 4, wherein: and in the step S5, drying is carried out in a drying box at 105 ℃.
6. The method for producing high-purity ammonium persulfate according to claim 5, wherein: in the step S6, refined titanium plating, copper plating and platinum plating are used as anodes, 0.03g of modified ammonium polyphosphate is added, and the electrolysis time is 4 hours.
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---|---|---|---|---|
CN107163292A (en) * | 2017-06-21 | 2017-09-15 | 广西壮族自治区化工研究院 | A kind of preparation method of ammonium polyphosphate modifying |
CN112301366A (en) * | 2020-10-30 | 2021-02-02 | 福建省展化化工有限公司 | Method for preparing ammonium persulfate based on titanium-based platinum anode electrode electrolysis method |
CN113174604A (en) * | 2021-04-13 | 2021-07-27 | 浙江工业大学 | Method for preparing sodium persulfate through direct electrooxidation |
CN113881952A (en) * | 2021-10-28 | 2022-01-04 | 浙江工业大学 | Electrolytic synthesis method of high sodium sulfate |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN107163292A (en) * | 2017-06-21 | 2017-09-15 | 广西壮族自治区化工研究院 | A kind of preparation method of ammonium polyphosphate modifying |
CN112301366A (en) * | 2020-10-30 | 2021-02-02 | 福建省展化化工有限公司 | Method for preparing ammonium persulfate based on titanium-based platinum anode electrode electrolysis method |
CN113174604A (en) * | 2021-04-13 | 2021-07-27 | 浙江工业大学 | Method for preparing sodium persulfate through direct electrooxidation |
CN113881952A (en) * | 2021-10-28 | 2022-01-04 | 浙江工业大学 | Electrolytic synthesis method of high sodium sulfate |
Non-Patent Citations (2)
Title |
---|
张招贤等.《钛电极学导论》.冶金工业出版社,2008,第706页. * |
电解法生产过硫酸铵的研究;赵建宏等;郑州大学学报(工学版);第109-112页 * |
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